European Journal of Organic Chemistry

Cover image for Vol. 2015 Issue 4

Early View (Online Version of Record published before inclusion in an issue)

Editor: Haymo Ross, Deputy Editor: Susan Wilkinson

Impact Factor: 3.154

ISI Journal Citation Reports © Ranking: 2013: 14/58 (Chemistry Organic)

Online ISSN: 1099-0690

Associated Title(s): Advanced Synthesis & Catalysis, Asian Journal of Organic Chemistry

VIEW

  1. 1 - 92
  1. Full Papers

    1. Low-Temperature Alkylation

      A Ruthenium-Based Catalytic System for a Mild Borrowing-Hydrogen Process

      Varsha R. Jumde, Luca Gonsalvi, Antonella Guerriero, Maurizio Peruzzini and Maurizio Taddei

      Article first published online: 30 JAN 2015 | DOI: 10.1002/ejoc.201403636

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      The alkylation of anilines with alcohols is possible at 55 °C using a Ru catalyst (2.5 mol-%) and a ligand that does not require an inert atmosphere.

    2. Pyrrole Derivatives

      One-Pot Directed Alkylation/Deprotection Strategy for the Synthesis of Substituted Pyrrole[3,4-d]pyridazinones

      Reji N. Nair and Thomas D. Bannister

      Article first published online: 29 JAN 2015 | DOI: 10.1002/ejoc.201403491

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      Optimized conditions were developed for a one-pot Boc-directed lithiation/alkylation reaction that also promoted in situ cleavage of the protecting group upon work-up. The efficiency of the process gave access to a number of compounds of interest as possible antitumor agents.

    3. Natural Products

      The Diels–Alder Approach to Δ9-Tetrahydrocannabinol Derivatives

      Franziska Gläser, Manuel C. Bröhmer, Thomas Hurrle, Martin Nieger and Stefan Bräse

      Article first published online: 29 JAN 2015 | DOI: 10.1002/ejoc.201403379

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      Molecules with structures similar to THC, such as nabilone, HU-210, or cannabidiol, show high pharmacological activities, and are used in chemotherapy or as appetite stimulants for AIDS patients. Therefore we have investigated various synthetic pathways using simple reaction methods to get access to a range of new THC derivatives.

    4. Organocatalysis

      Organocatalytic Conjugate Addition of Cyclopropylacetaldehyde Derivatives to Nitro Olefins: en Route to β- and γ-Amino Acids

      Mikk Kaasik, Artur Noole, Kärt Reitel, Ivar Järving and Tõnis Kanger

      Article first published online: 29 JAN 2015 | DOI: 10.1002/ejoc.201403387

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      Cyclopropane-containing amino acids can be synthesised through an organocatalytic asymmetric Michael reaction. The cyclopropane ring, as well as two different nitrogen-containing functional groups (tert-butoxycarbonylamino and nitro) are introduced in one step. The products were isolated in good yields with moderate to excellent enantio- and diastereoselectivities.

    5. Carbon Nanotubes

      Covalent Functionalization of Carbon Nanotubes with Xanthates and Peroxides

      Florence Pennetreau, Charles Vriamont, Béatrice Vanhorenbeke, Olivier Riant and Sophie Hermans

      Article first published online: 29 JAN 2015 | DOI: 10.1002/ejoc.201403545

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      Xanthates were used as versatile and readily available substrates for covalent sidewall functionalizations of carbon nanotubes (CNTs). The grafting of seven different xanthates onto the CNT surface by using peroxides as a radical initiator revealed the one-pot double functionalization by both xanthate and peroxide moieties. This method provides ready-to-use CNTs for postfunctionalization reactions.

  2. Short Communications

    1. Multicomponent Reactions

      FeCl3-Catalyzed SF5-Containing Quinoline Synthesis: Three-Component Coupling Reactions of SF5-Anilines, Aldehydes and Alkynes

      Xueling Mi, Jing Chen and Lijin Xu

      Article first published online: 29 JAN 2015 | DOI: 10.1002/ejoc.201403613

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      The iron-catalyzed three-component coupling/hydroarylation/dehydrogenation reaction of SF5-anilines, aldehydes and alkynes provides an efficient route to SF5-containing quinolines.

  3. Microreviews

    1. Green Chemistry

      Chitosan: An Upgraded Polysaccharide Waste for Organocatalysis

      Olivier Mahé, Jean-François Brière and Isabelle Dez

      Article first published online: 29 JAN 2015 | DOI: 10.1002/ejoc.201403396

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      This microreview outlines recent advances in achiral to asymmetric organocatalytic reactions based on chitosan, a biodegradable chiral polysaccharide obtained from marine wastes, in a sustainable chemistry context. The use of chitosan and its derivatives either as insoluble organocatalysts or as supports for organocatalysts is reviewed, together with shaping and reusability issues.

  4. Full Papers

    1. Cross-Coupling of Heterocycles

      Visible-Light-Photocatalyzed Metal-Free C–H Heteroarylation of Heteroarenes at Room Temperature: A Sustainable Synthesis of Biheteroaryls

      Pintu Maity, Debasish Kundu and Brindaban C. Ranu

      Article first published online: 29 JAN 2015 | DOI: 10.1002/ejoc.201500006

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      An efficient C–H heteroarylation of heteroarenes is achieved through visible-light photoredox-catalyzed diazotization of heteroarylamines in situ by tBuONO at room temperature in the absence of any transition metal, additive, or acid. The approach gives access to a library of functionalized biheteroaryls.

    2. Structural Hybrid Synthesis

      Synthesis of Antitumor Carbazole-Amonafide Structural Hybrids

      Alex Rozovsky, Elena Regozin, Mor Oron-Herman, Amnon Albeck and Gary Gellerman

      Article first published online: 29 JAN 2015 | DOI: 10.1002/ejoc.201403549

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      A facile synthesis of new [4,5-bc]carbazole-amonafide derivatives with selective antitumor activity is described. This new class of structural hybrids contains the medicinally important carbazole and amonafide cores.

    3. Porphyrinoids

      Regioselective Nucleophilic Aromatic Substitution Reaction of meso-Pentafluorophenyl-Substituted Porphyrinoids with Alcohols

      Hartwig R. A. Golf, Hans-Ulrich Reissig and Arno Wiehe

      Article first published online: 28 JAN 2015 | DOI: 10.1002/ejoc.201403503

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      Readily available meso-pentafluorophenyl-substituted porphyrins and corroles can be functionalized at the para position with alcohols in regioselective SNAr reactions to give high yields under optimized conditions. The method has been applied to steroids as well as enantiopure and highly fluorinated alcohols. With suitable protecting groups, functionalized, polar A3B porphyrins are accessible.

    4. Organochalcogen Compounds

      Nucleophilic Cyclization of o-Alkynylbenzamides Promoted by Iron(III) Chloride and Diorganyl Dichalcogenides: Synthesis of 4-Organochalcogenyl-1H-isochromen-1-imines

      Jose S. S. Neto, Davi F. Back and Gilson Zeni

      Article first published online: 27 JAN 2015 | DOI: 10.1002/ejoc.201403534

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      4-Organochalcogenyl-1H-isochromen-1-imines are prepared by treatment of o-alkynylbenzamides with a combination of iron salts and diorganyl dichalcogenides in an electrophile-promoted nucleophilic cyclization.

    5. Natural Product Synthesis

      First Total Synthesis of Piperenol B and Configuration Revision of the Enantiomers Piperenol B and Uvarirufol A

      Thomas C. Fischer, Bruno Cerra, Michael J. Fink, Florian Rudroff, Ernst Horkel and Marko D. Mihovilovic

      Article first published online: 27 JAN 2015 | DOI: 10.1002/ejoc.201403582

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      The first total synthesis of piperenol B, a polyoxygenated cyclohexene natural product from Piper cubeb, has been developed starting with the multi-ten-gram scale enzymatic dihydroxylation of sodium benzoate. The originally predicted absolute configurations of piperenol B and its enantiomer uvarirufol A were eventually revised based on this synthesis and NMR analysis of late-stage Mosher's esters.

  5. Short Communications

    1. Oxidative Amidation

      Iodine-Promoted Oxidative Amidation of Terminal Alkenes – Synthesis of α-Ketoamides, Benzothiazoles, and Quinazolines

      Ramesh Deshidi, Shekaraiah Devari and Bhahwal Ali Shah

      Article first published online: 27 JAN 2015 | DOI: 10.1002/ejoc.201403547

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      A novel metal-free strategy for oxidative amidation of terminal alkenes using I2/DMSO for the synthesis of α-ketoamides has been developed. Intriguingly, the use of tert-butylhydroperoxide (TBHP) as co-oxidant can facilitate the synthesis of α-ketoamides at room temperature without any solvent, whereas for reaction with primary amines SeO2 is required as oxidizing agent.

    2. Protecting Groups

      Fmox: A Base-Labile Aldehyde Protecting Group

      Frederik Diness and Morten Meldal

      Article first published online: 27 JAN 2015 | DOI: 10.1002/ejoc.201403643

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      The Fmox group [3-Fmoc-(1,3)-oxazinane] is a novel base-labile protecting group for the protection of aldehydes while manipulating other functional groups e.g., amines. It is completely removed under mild basic conditions under which a range of other aldehyde protecting groups are fully stable. Studies on the introduction and removal of Fmox and other aldehyde protecting groups have provided new mechanistic insight.

  6. Full Papers

    1. β-Amino Esters

      Studies on N-Activation for the Lipase-Catalyzed Enantioselective Preparation of β-Amino Esters from 4-Phenylazetidin-2-one

      Riku Sundell and Liisa T. Kanerva

      Article first published online: 27 JAN 2015 | DOI: 10.1002/ejoc.201403467

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      The effect of N-substitution on the enantioselective lipase-catalyzed ring-opening of 4-phenylazetidin-2-one was examined by alcoholysis reactions in dry organic solvents. The nature of the N-substituent dramatically affected the reactivity of the β-lactam. Through this approach, N-acylated β-amino esters were formed in good yields and with excellent enantiopurity.

    2. Radical Reactions

      Copper-Catalysed Alkylarylation of Activated Alkenes Using AIBN and Beyond: An Access to Cyano-Containing Oxindoles

      Dong Zhou, Zi-Hao Li, Jie Li, Shu-Hua Li, Ming-Wei Wang, Xiao-Ling Luo, Guo-Liang Ding, Rui-Long Sheng, Mei-Jun Fu and Shi Tang

      Article first published online: 27 JAN 2015 | DOI: 10.1002/ejoc.201403499

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      A copper-catalysed oxidative radical alkylarylation of activated alkenes using azobisisobutyronitrileand related compounds has been developed. Oxindoles with primary, and tertiary nitrile moieties at the 3-position were synthesized efficiently by a cascade addition/C(sp2)–H cyclization process.

  7. Short Communications

    1. Photochromism

      Photochromism of Acetyl-Cyclophanochromene: Intriguing Stabilization of Photogenerated Colored o-Quinonoid Intermediates

      Susovan Mandal, Arindam Mukhopadhyay and Jarugu Narasimha Moorthy

      Article first published online: 27 JAN 2015 | DOI: 10.1002/ejoc.201403403

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      A combination of the phane effect, that is, through-space π-electron delocalization, and electrophile···nucleophile interactions results in remarkable persistence of the photogenerated colored o-quinonoid intermediate of acetyl-cyclophanochromene.

  8. Full Papers

    1. Nitrogen Heterocycles

      Silver-Mediated Cα(sp3)–H Functionalization of Primary Amines: An Oxidative C–N Coupling Strategy for the Synthesis of Two Different Types of 1,2,4,5-Tetrasubstituted Imidazoles

      Rajib Sarkar and Chhanda Mukhopadhyay

      Article first published online: 26 JAN 2015 | DOI: 10.1002/ejoc.201403465

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      A new silver(I)-mediated Cα(sp3)–H bond functionalization of primary amines followed by an oxidative C–N cross-coupling reaction to form highly diverse 1,2,4,5-tetrasubstituted imidazoles has been demonstrated. This protocol provides a simple, highly efficient, and straightforward approach, which is promoted by a silver species, to give the products in good to excellent yields.

    2. Conformational Probes

      Stereoselective Synthesis of Boat-Locked Glycosides Designed as Glycosyl Hydrolase Conformational Probes

      Emilie Thiery, Jérémy Reniers, Johan Wouters and Stéphane P. Vincent

      Article first published online: 26 JAN 2015 | DOI: 10.1002/ejoc.201403363

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      A general method for the preparation of galactose derivatives locked in a 1,4B boat conformation has been developed. The boat scaffold was stereoselectively functionalized at the C-1′ position by aliphatic and aromatic groups along with azido or hydroxy groups. These molecules have been designed to probe the conformational itinerary of the substrate of glycosyl-processing enzymes.

  9. Short Communications

    1. Synthesis of Isoxazolines

      Oxime-Mediated Oxychlorination and Oxybromination of Unactivated Olefins

      Kui-Yong Dong, Hai-Tao Qin, Feng Liu and Chen Zhu

      Article first published online: 23 JAN 2015 | DOI: 10.1002/ejoc.201403538

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      One to two: An oxime-mediated oxychlorination and oxybromination of unactivated olefins relying on palladium catalysis has been developed. A wide range of chlorinated and brominated isoxazolines has been synthesized in moderate to good yields.

  10. Full Papers

    1. Amination

      Copper-Catalyzed Direct Amination of 1,2,3-Triazole N-Oxides by C–H Activation and C–N Coupling

      Jiayi Zhu, Yubo Kong, Feng Lin, Baoshuang Wang, Zhengwang Chen and Liangxian Liu

      Article first published online: 23 JAN 2015 | DOI: 10.1002/ejoc.201403583

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      A facile, efficient, and practical method for the copper-catalyzed direct C–H amination of 2-aryl-1,2,3-triazole N-oxides with various amines, including primary and secondary aliphatic and aromatic amines, has been developed. Furthermore, the targeted N+–O bond cleavage is observed during the reaction and, thus, an additional deoxygenation step is obviated.

    2. Sulfonamides from Sulfinates

      Iodine-Catalyzed Oxidative Amination of Sodium Sulfinates: A Convenient Approach to the Synthesis of Sulfonamides under Mild Conditions

      Chonchanok Buathongjan, Danupat Beukeaw and Sirilata Yotphan

      Article first published online: 23 JAN 2015 | DOI: 10.1002/ejoc.201403531

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      A convenient synthesis of sulfonamides from sodium sulfinates and amines in the presence of catalytic iodine and sodium percarbonate as oxidant is described. This reaction proceeds under mild conditions, tolerates a wide range of functionalities, and provides a series of sulfonamide products in moderate to good yields.

    3. Odorants

      Structure–Activity Relationships in the Domain of Odorants Having Marine Notes

      Jean-Marc Gaudin and Jean-Yves de Saint Laumer

      Article first published online: 23 JAN 2015 | DOI: 10.1002/ejoc.201403365

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      A new class of molecules having marine, watery olfactory notes has been discovered. A model built from the Calone 1951® family shows that the seven-membered ring with a ketone group can be replaced by a five-membered ring bearing an aldehyde. Interestingly, as a side benefit, a methyl carbonate compound has been synthesized that is olfactively very close to vanillin and has interesting properties.

  11. Short Communications

    1. Fullerenes

      Efficient Microwave-Assisted Synthesis of PCBM Methanofullerenes (C60 and C70)

      Caroline Hadad, Zois Syrgiannis, Aurelio Bonasera and Maurizio Prato

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejoc.201403563

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      PC61BM and PC71BM fullerene mono-adducts, and also a series of bis-adduct PCBM-like derivative mixtures, were successfully prepared by a one-step cyclopropanation reaction under microwave irradiation. All products were obtained in good yields, in short time, during which isomerization of the open [5,6] to the closed [6,6] form takes place in situ.

    2. Helicene Synthesis

      Enantioselective Synthesis, Crystal Structure, and Photophysical Properties of a 1,1′-Bitriphenylene-Based Sila[7]helicene

      Koichi Murayama, Yasuaki Oike, Seiichi Furumi, Masayuki Takeuchi, Keiichi Noguchi and Ken Tanaka

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejoc.201403565

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      A 1,1′-bitriphenylene-based sila[7]helicene was synthesized with a high ee value by enantioselective double [2+2+2] cycloaddition of a biaryl-linked tetrayne and a silicon-linked bis(propargylic alcohol) as a key step. This sila[7]helicene exhibited a relatively high fluorescence quantum yield and circularly polarized luminescence activity.

    3. Fluorescent Sensors

      Improved Synthesis of the Triazacryptand (TAC) and its Application in the Construction of a Fluorescent TAC-BODIPY Conjugate for K+ Sensing in Live Cells

      Binglin Sui, Xiling Yue, Michael G. Tichy, Taihong Liu and Kevin D. Belfield

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejoc.201403600

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      The dye, TAC-BODIPY, emits very weak fluorescence at 512 nm. Upon binding with K+, it becomes highly fluorescent, emitting very strong fluorescence. TAC-BODIPY exhibits excellent selectivity toward K+ over Na+ and desirable sensitivity for K+ sensing. This fluorescent K+ sensor is capable of efficiently sensing the K+ levels in living cells through cell imaging with fluorescence microscopy.

  12. Full Papers

    1. Alkyl Sulfinates

      Alkyl Sulfinates: Formal Nucleophiles for Synthesizing TosMIC Analogs

      J. Armando Lujan-Montelongo, Angel Ojeda Estevez and Fraser F. Fleming

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejoc.201403615

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      Alkyl sulfinates function as formal nucleophiles in Mannich reactions. Dehydration of the resulting N-(sulfonylmethyl)formamides gives TosMIC [(tolylsulfonyl)methyl isocyanide] analogs in an efficient two-step synthesis. The strategy provides a rapid, general, and efficient synthesis of sulfonylmethyl isonitriles by formally reversing the usual role of alkyl sulfinates as electrophiles.

    2. Thiodisaccharide Sulfoxides

      Thiodisaccharide Sulfoxides: Absolute Configuration of the SO Sulfur Atom and Influence on the Biological Activity towards the β-Galactosidase from E. coli

      Juan P. Colomer, María Ángeles Canales Mayordomo, Beatriz Fernández de Toro, Jesús Jiménez-Barbero and Oscar Varela

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejoc.201403609

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      The absolute configurations of the sulfur stereocenters of (1[RIGHTWARDS ARROW]4)-thiodisaccharide S-oxides have been assigned on the basis of the NMR chemical shifts of the β protons with respect to the S=O group (3-H and 5-H). Each diastereoisomer displays different biological activities, as inhibitors or substrates, of the β-galactosidase from E. coli.

    3. Cross-Coupling

      Copper-Catalyzed Asymmetric Oxidative Cross-Coupling of 2-Naphthols with Aryl Methyl Ketones

      Tao Deng, Hongjun Wang and Chun Cai

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejoc.201403512

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      A copper-catalyzed asymmetric oxidative cross-coupling reaction of 2-naphthols with aryl methyl ketones is presented. This transformation provides an efficient route to various functionalized naphtho[2,1-b]furan-1(2H)-ones in an enantiomerically enriched manner with molecular oxygen in air as the oxidant.

    4. Dibenz[a,c]anthracenes

      Synthesis of Substituted Dibenz[a,c]anthracenes and an Investigation of Their Liquid-Crystalline Properties

      Katie M. Psutka, Joshua Williams, Joseph A. Paquette, Oliver Calderon, Kevin J. A. Bozek, Vance E. Williams and Kenneth E. Maly

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejoc.201403504

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      The synthesis of a series of novel dibenz[a,c]anthracenes is described. The dicyano-substituted derivatives exhibit columnar mesophases and are consistent with antiparallel stacking and a tilted arrangement within the columns.

  13. Microreviews

    1. Continuous Flow Catalysts

      Organocatalysis on Tap: Enantioselective Continuous Flow Processes Mediated by Solid-Supported Chiral Organocatalysts

      Carles Rodríguez-Escrich and Miquel A. Pericàs

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejoc.201403042

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      Modern continuous flow techniques are reshaping the chemical landscape by providing tools for more efficient chemical processes. Enantioselective catalysis can also benefit from these advantages, and the combination of these two fields is a perfect match in terms of sustainable chemistry. Here we focus on the use of immobilized organocatalysts to promote enantioselective processes in flow.

  14. Full Papers

    1. Energetic Materials

      4,4,8,8-Tetranitroadamantane-2,6-diyl Dinitrate: A High-Density Energetic Material

      Yifei Ling, Xiaoli Ren, Weipeng Lai and Jun Luo

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejoc.201403449

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      The novel high-performance energetic material 4,4,8,8-tetranitroadamantane-2,6-diyl dinitrate has been synthesized by the formylation of 1,5-cyclooctanedione followed by intramolecular aldol condensation to construct the adamantane skeleton.

  15. Microreviews

    1. Furopyridines

      Elaboration of Furopyridine Scaffolds

      Adeline Jasselin-Hinschberger, Corinne Comoy, Anthony Chartoire and Yves Fort

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejoc.201403412

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      This review is focused on furopyridines and especially on the different strategies that allow their synthesis.

  16. Full Papers

    1. 1,3-Dipolar Cycloaddition

      Unprotected Xylose-Derived Nitrone in Stereodivergent Synthesis of 4-Hydroxypiperidine Enantiomers: Weak Lewis Acid Induced Alteration of Stereochemistry in 1,3-Dipolar Cycloaddition

      Tomasz Rowicki, Maciej Malinowski, Maciej Gryszel, Karolina Czerwińska, Izabela Madura, Ewa Mironiuk-Puchalska, Mariola Koszytkowska-Stawińska and Wojciech Sas

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejoc.201403410

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      A one-pot, two-step synthesis of chiral 7-oxa-1-azabicyclo[2.2.1]heptane derivatives from unprotected D-xylose was achieved by an intramolecular 1,3-dipolar cycloaddition of the N-(γ-alkenyl)-substituted nitrone intermediate. The stereochemical course of the reaction was altered by the addition of an achiral Lewis acid. The bicyclic byproducts were used to prepare two new enantiomeric piperidine-type iminosugars.

    2. Organozinc Chemistry

      Variations in the Blaise Reaction: Conceptually New Synthesis of 3-Amino Enones and 1,3-Diketones

      H. Surya Prakash Rao and Nandurka Muthanna

      Article first published online: 22 JAN 2015 | DOI: 10.1002/ejoc.201403402

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      A variety of aryl/heteroaryl/alkyl nitriles were converted into 3-amino enones or 1,3-diketones by reaction with 2-bromoethanones in the presence of zinc under Blaise reaction conditions. The commercially important product avobenzone was synthesized.

    3. Natural Products

      An Enantioselective Synthesis of (R)-5,6-Octadecadienoic Acid

      Qiong Yu and Shengming Ma

      Article first published online: 20 JAN 2015 | DOI: 10.1002/ejoc.201403588

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      The scalable total synthesis of naturally occurring (R)-5,6-octadecadienoic acid was carried out in 12 % overall yield with an enantiomeric excess (ee) value of 98 % by using TBS-protected (TBS = tert-butyldimethylsilyl) propargyl alcohol and n-dodecanal with (R)-α,α-diphenylprolinol as the chiral source.

    4. Flow Chemistry

      Generation and Trapping of Ketenes in Flow

      Cyril Henry, David Bolien, Bogdan Ibanescu, Sally Bloodworth, David C. Harrowven, Xunli Zhang, Andy Craven, Helen F. Sneddon and Richard J. Whitby

      Article first published online: 20 JAN 2015 | DOI: 10.1002/ejoc.201403603

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      Ketenes are generated under flow conditions by thermal sigmatropic rearrangement of alkoxyalkynes. Subsequent trapping with amines or alcohols gives amide or ester products, respectively. Inline monitoring by IR spectroscopy and offline analysis by 1H NMR spectroscopy allow the rapid study of kinetics and optimisation of the reaction.

  17. Short Communications

    1. Hydroamination

      Formal Intermolecular Hydroamination of Unbiased Olefins for Primary Amine Formation

      Yongsheng Yang, Nurul Imma Wong and Peili Teo

      Article first published online: 20 JAN 2015 | DOI: 10.1002/ejoc.201403654

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      A Pd/Ir catalyst system catalyzes the one-pot, two-step formal hydroamination of unbiased olefins with an ammonia source to give branched primary amines in high yields by using only 1 mol-% of the catalyst. Various lactams, α-amines, and secondary amines can also be prepared. This is the first report of the formal one-pot intermolecular hydroamination of olefins to obtain primary amines.

  18. Full Papers

    1. Metathesis Chemistry

      Synthesis of Acyloxy-Semicyclic Dienes Using an Enyne Metathesis/Ring Closing Metathesis Approach

      Jui Thiang Brian Kueh, Lindon W. K. Moodie, Nigel T. Lucas and David S. Larsen

      Article first published online: 20 JAN 2015 | DOI: 10.1002/ejoc.201403482

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      An enyne metathesis/ring closing metathesis (EM/RCM) sequence was developed to allow convenient access to acyloxy-semicyclic dienes not available from the cross metathesis of vinyl esters with the termini of 1,3-dienes. The prepared acyloxy-semicyclic dienes constitute useful reactants in Diels–Alder cycloadditions.

    2. Reductive Iodination

      One-Pot Preparation of Alkyl Iodides from Esters by Indium-Catalyzed Reductive Cleavage of a Carbon–Oxygen Bond

      Norio Sakai, Yohei Matsushita, Takeo Konakahara, Yohei Ogiwara and Keisuke Hirano

      Article first published online: 20 JAN 2015 | DOI: 10.1002/ejoc.201403539

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      Indium tribromide effectively catalyzed the reductive iodination of esters to produce the corresponding alkyl iodides. A range of aliphatic and aromatic esters underwent the reaction, as did ester moieties in polymers.

    3. Scaffold-Oriented Synthesis

      Efficient Use of 1,2-Dihaloazine Synthons in Transition-Metal-Free Preparation of Diverse Heterocycle-Fused 1,4-Oxazepines

      Alexander V. Sapegin, Stanislav A. Kalinin, Alexey V. Smirnov, Mikhail V. Dorogov and Mikhail Krasavin

      Article first published online: 19 JAN 2015 | DOI: 10.1002/ejoc.201403397

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      Ambiphilic 2-(1H-pyrazol-5-yl)phenols underwent an efficient condensation reaction with a variety of 1,2-dihaloazines to afford heterocycle-fused 1,4-oxazepines. The reaction is thought to involve sequential SNAr/Smiles rearrangement/SNAr reactions. The participation of 3-bromo-2-chloropyridines in this transition-metal-free protocol was unexpected.

    4. Geminal Acylation

      Two Rearrangement Pathways in the Geminal Acylation of 2-Methoxyoxazolidines Leading to Substituted 1,4-Oxazines

      Jonathan R. Moulins, Jeremy A. Hughes, Lauren E. Doyle, T. Stanley Cameron and D. Jean Burnell

      Article first published online: 19 JAN 2015 | DOI: 10.1002/ejoc.201403371

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      The course of BF3-mediated geminal acylation of cyclic orthoamides with five- and six-membered acyloins was altered by carrying out the second rearrangement step with, or without, added water. Subsequent heterocyclization afforded isomeric cyclopenta- and cyclohexa[b][1,4]oxazinones in yields of 30 to 73 % over three steps.

    5. Diastereoselective Cyclizations

      Diastereodivergent Pictet–Spengler Cyclization of Bicyclic N-Acyliminium Ions: Controlling a Quaternary Stereocenter

      Benoît de Carné-Carnavalet, Jean-Philippe Krieger, Benoît Folléas, Jean-Louis Brayer, Jean-Pierre Demoute, Christophe Meyer and Janine Cossy

      Article first published online: 19 JAN 2015 | DOI: 10.1002/ejoc.201403469

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      The diastereoselectivity of the Pictet–Spengler cyclization of bicyclic N-acyliminium ions that have a 3-azabicyclo[n.3.0]alkane core and an electron-rich π-nucleophilic moiety (indol-2-yl, indol-3-yl, 1-methylpyrrol-2-yl, or 3,5-dimethoxyphenyl group) was examined. Control of the new quaternary stereocenter was achieved in a diastereodivergent manner by fine-tuning the reaction conditions.

    6. Atropisomerism

      Elucidating the Structural Isomerism of Fluorescent Strigolactone Analogue CISA-1

      Hannelore Goossens, Thomas S. A. Heugebaert, Busra Dereli, Melissa Van Overtveldt, Ozlem Karahan, Ilknur Dogan, Michel Waroquier, Veronique Van Speybroeck, Viktorya Aviyente, Saron Catak and Christian V. Stevens

      Article first published online: 19 JAN 2015 | DOI: 10.1002/ejoc.201403457

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      The occurrence of atropisomers among strigolactone analogues is reported for the first time. While the rate of interconversion for this specific derivative is sufficiently high to warrant full bioavailability, these findings are of high importance for the development of new analogues that could lead to stable atropisomers with different bioactivity.

  19. Short Communications

    1. Perfluoroalkylation

      Perfluoroalkylation of Nitrones for the Synthesis of a Series of Fucosidase Inhibitors

      Jadwiga Paszkowska, Olalla Novo Fernandez, Ilona Wandzik, Stéphanie Boudesoque, Laurent Dupont, Richard Plantier-Royon and Jean-Bernard Behr

      Article first published online: 19 JAN 2015 | DOI: 10.1002/ejoc.201403485

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      Iminosugars featuring a fluoroalkyl chain in the pseudoanomeric position are synthesized by nucleophilic addition of a perfluoroalkyl Grignard reagent to a nitrone. Reduction of the N–O bond of the hydroxylamine is achieved by treatment with aqueous SO2. Inhibitory potencies of the fluorinated iminosugars and their corresponding hydroxylamines are evaluated against α-L-fucosidase at various pH values.

    2. Pd-Catalyzed Arylation

      Palladium-Catalyzed Desulfitative Arylation of 5-Alkoxy-3,4-dibromo-2(5H)-furanone with Sodium Arylsulfinates

      Jie Shi, Xiao-Dong Tang, Yan-Cheng Wu, Hua-Nv Li, Liu-Juan Song and Zhao-Yang Wang

      Article first published online: 19 JAN 2015 | DOI: 10.1002/ejoc.201403404

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      A palladium-catalyzed desulfitative arylation reaction of 5-alkoxy-3,4-dibromo-2(5H)-furanone to provide 5-alkoxy-4-aryl-3-bromo-2(5H)-furanone has been reported. Various sodium arylsulfinates as cheap and easily available aryl sources are well tolerated under the mild reaction conditions.

  20. Microreviews

    1. Biologically Active Sesquiterpenes

      Trends in the Synthesis and Functionalization of Guaianolides

      Alejandro Santana, José M. G. Molinillo and Francisco A. Macías

      Article first published online: 15 JAN 2015 | DOI: 10.1002/ejoc.201403244

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      Guaianolides and their derivatives display diverse biological activities and have for decades been targets for synthesis. Semi-synthesis, usually staring from eudemane sesquiterpenes, or total synthesis by use of an extensive range of synthetic methodologies to obtain the hydroazulene skeleton are the two principal strategies.

  21. Full Papers

    1. Sultams

      A Route to Benzo-Annelated δ-Sultams through Michael Cyclization

      Daria S. Grosheva, Valentin A. Rassadin and Victor V. Sokolov

      Article first published online: 15 JAN 2015 | DOI: 10.1002/ejoc.201403416

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      The method described involves Michael cyclization of sulfonamides, and gives access to a wide range of benzo-annelated six-membered sultams.

  22. Short Communications

    1. Nitroheterocycles

      Tailor-Made Synthesis of N,N,2,6-Tetrasubstituted 4-Nitroanilines by Three-Component Ring Transformation of Dinitropyridone

      Song Thi Le, Haruyasu Asahara and Nagatoshi Nishiwaki

      Article first published online: 15 JAN 2015 | DOI: 10.1002/ejoc.201403652

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      The ring transformation of dinitropyridone afforded various kinds of N,N,2,6-tetrasubstituted 4-nitroanilines, of which the benzene ring as well as the amino group was easily modified by only changing a ketone and an amine.

  23. Full Papers

    1. Computational NMR Methods

      Computational NMR Methods in the Stereochemical Analysis of Organic Compounds: Are Proton or Carbon NMR Chemical Shift Data More Discriminating?

      Maria Giovanna Chini, Raffaele Riccio and Giuseppe Bifulco

      Article first published online: 15 JAN 2015 | DOI: 10.1002/ejoc.201403569

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      The use of 1H NMR DFT calculations is a better choice than the corresponding 13C NMR calculations for assigning the relative configurations of organic compounds.

    2. Organocatalysis

      Solvent-Induced Reversal of Enantioselectivity in the Synthesis of Succinimides by the Addition of Aldehydes to Maleimides Catalysed by Carbamate-Monoprotected 1,2-Diamines

      Jesús Flores-Ferrándiz, Béla Fiser, Enrique Gómez-Bengoa and Rafael Chinchilla

      Article first published online: 15 JAN 2015 | DOI: 10.1002/ejoc.201403415

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      An inversion of enantioselectivity is achieved by simply changing the solvent in the enantioselective Michael addition reaction of aldehydes to maleimides catalysed by carbamate-monoprotected trans-cyclohexane-1,2-diamines. The reasons behind this uncommon enantioswitch are explained using theoretical calculations.

    3. Cycloaddition Reactions

      Pericyclic Reactions of Azafulvenium Methides Bearing Internal Dipolarophiles – Synthesis of Chromene and Chromane Derivatives

      Fernanda M. Ribeiro Laia, Maria I. L. Soares, Clara S. B. Gomes and Teresa M. V. D. Pinho e Melo

      Article first published online: 15 JAN 2015 | DOI: 10.1002/ejoc.201403407

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      The microwave-induced thermolysis of 1H,3H-pyrrolo[1,2-c]thiazole 2,2-dioxides substituted at C-3 with allyloxyphenyl and prop-2-ynyloxyphenyl groups was studied. These sulfones underwent extrusion of SO2 to afford azafulvenium methides, which participated in pericyclic reactions to afford 2-[2-(2H-chromen-8-yl)vinyl]-1H-pyrroles and heterocycle-fused chromenes and chromanes.

    4. Host–Guest Systems

      Linker-Length-Dependent Complexation of a Triptycene-Derived Macrotricyclic Polyether with π-Extended Viologens

      Ying Han, Ya-Kun Gu, Jia-Bin Guo and Chuan-Feng Chen

      Article first published online: 15 JAN 2015 | DOI: 10.1002/ejoc.201403390

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      Complexation between a triptycene-derived macrotricyclic polyether and π-extended viologens with different linker lengths in both the solution and the solid state was investigated in detail. It was found that the macrotricyclic host could form complexes in multiple complexation modes with π-extended viologens of different linker lengths.

    5. Natural Products

      Synthesis of the Azaoxoaporphine Alkaloid Sampangine and Ascididemin-Type Pyridoacridines through TMPMgCl·LiCl-Mediated Ring Closure

      Alois Plodek, Mathias König and Franz Bracher

      Article first published online: 14 JAN 2015 | DOI: 10.1002/ejoc.201403502

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      A new approach to sampangine and various ring A analogues and isomers of the pyridoacridine alkaloid ascididemin is described. Ring A scaffolds bearing an ester moiety in the ortho position were introduced through Suzuki or Neghishi cross-coupling reactions. The final cyclization step was achieved through a directed remote ring metallation with the Knochel–Hauser base.

    6. Ring-Expanded Nucleosides

      Diastereoselective Synthesis of (1,3-Dioxan-4-yl)pyrimidine and Purin Nucleoside Analogues

      Umberto M. Battisti, Claudia Sorbi, Antonio Quotadamo, Silvia Franchini, Annalisa Tait, Dominique Schols, Lak Shin Jeong, Sang Kook Lee, Jayoung Song and Livio Brasili

      Article first published online: 14 JAN 2015 | DOI: 10.1002/ejoc.201403473

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      The first regioselective and diastereoselective synthesis of 1,3-dioxan-4-yl-substituted nucleoside analogues is reported. (4-Acetoxy-1,3-dioxan-2-yl)methyl benzoate is regioselectively glycosylated under Vorbrüggen conditions to afford the desired products in good yields. The regioselectivity might be due to the existence of thermodynamically controlled intermediates.

  24. Short Communications

    1. Glycosylation

      Palladium-Catalyzed Stereoselective C-Glycosylation of Glycals with Sodium Arylsulfinates

      Jimei Ma, Shaohua Xiang, Hong Jiang and Xue-Wei Liu

      Article first published online: 12 JAN 2015 | DOI: 10.1002/ejoc.201403550

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      A desulfitative C-glycosylation strategy between commercially available glycals and sodium arylsulfinates is investigated. The C-aryl glycosides are formed by palladium-catalyzed Ferrier-type coupling with high regioselectivity and stereoselectivity.

  25. Full Papers

    1. Ti-Mediated Aldol Addition

      From Amino Acids to Fluorine-Containing Carbohydrates: De Novo Synthesis of 2-Amino-4-Fluoroxylose and -lyxose

      Christopher Albler and Walther Schmid

      Article first published online: 12 JAN 2015 | DOI: 10.1002/ejoc.201403532

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      Fluorinated derivatives of amino-xylose and -lyxose have been prepared by aldolization of D- and L-cysteine-derived aldehydes and a fluoroacetyl ephedrine oxazolidinone auxiliary. Photochemical Pummerer-type rearrangement followed by acidic cleavage of the protecting groups subsequently furnished the title compounds in overall yields of 47–48 % over four steps.

    2. Fluorinated Compounds

      Synthesis of Trifluoromethylated Analogues of 4,5-Dihydroorotic Acid

      Volodymyr A. Sukach, Anastasia A. Resetnic, Viktor M. Tkachuk, Zhengguo Lin, Ulrich Kortz, Mykhailo V. Vovk and Gerd-Volker Röschenthaler

      Article first published online: 12 JAN 2015 | DOI: 10.1002/ejoc.201403495

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      A preparatively convenient route to trifluoromethylated analogues of 4,5-dihydroorotic acid and their esters featuring intramolecular orthogonal dipolar C–F···C=O interactions in the crystal state is presented.

    3. Hydrostannylation–Cross-Coupling

      Hydrostannylation–Cross-Coupling Strategy for the Stereoselective Synthesis of Alkylidenemalonates and Related α,β-Unsaturated Esters

      Shinichi Fujiwara, Romain Cadou, Yousuke Yamaoka, Kiyosei Takasu and Ken-ichi Yamada

      Article first published online: 12 JAN 2015 | DOI: 10.1002/ejoc.201403429

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      Pd-catalyzed and radical hydrostannylation of propiolate derivatives stereoselectively provided α-alkoxycarbonyl (E)- and (Z)-vinylstannanes, respectively, which were then converted into alkylidenemalonates by the Stille coupling reaction. A one-pot process was also realizable for the Pd-catalyzed reactions.

    4. Peptidomimetics

      Stereocontrolled One-Step Synthesis of Difunctionalised Cispentacin Derivatives through Ring-Opening Metathesis of Norbornene β-Amino Acids

      Loránd Kiss, Márton Kardos, Enikő Forró and Ferenc Fülöp

      Article first published online: 9 JAN 2015 | DOI: 10.1002/ejoc.201403493

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      Through the ring-opening metathesis of norbornene or oxanorbornene β-amino acids with ethylene in the presence of certain Ru catalysts, a convenient stereocontrolled one-step method was devised for the preparation of divinylated cispentacins and oxacyclic cispentacin stereoisomers with four chiral centres.

    5. [2+2+2] Cycloaddition

      Synthesis of Pyridylphosphonates by Rhodium-Catalyzed [2+2+2] Cycloaddition of 1,6- and 1,7-Diynes with Diethyl Phosphorocyanidate

      Kenichi Kashima, Masahiro Ishii and Ken Tanaka

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejoc.201403452

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      The convenient and atom-economical synthesis of substituted bicyclic pyridylphosphonates has been achieved by the cationic rhodium(I)/H8-binap-complex-catalyzed [2+2+2] cycloaddition of 1,6- and 1,7-diynes with diethyl phosphorocyanidate. These reactions may proceed via an azarhodacyclopentadiene intermediate in addition to the rhodacyclopentadiene intermediate.

    6. Sponge Natural Products

      Dysifragilones A–C, Unusual Sesquiterpene Aminoquinones and Inhibitors of NO Production from the South China Sea Sponge Dysidea fragilis

      Wei-Hua Jiao, Ting-Ting Xu, Feng Zhao, Hao Gao, Guo-Hua Shi, Jie Wang, Li-Li Hong, Hao-Bing Yu, Yu-Shan Li, Fan Yang and Hou-Wen Lin

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejoc.201403487

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      Dysifragilones A–C (13), three unusual sesquiterpene aminoquinones based on a rearranged avarone skeleton, were isolated from the marine sponge Dysidea fragilis. Their structures were determined by spectroscopy and from calculated ECD spectra. Dysifragilone A (1) showed potent inhibitory activity on NO production stimulated by LPS in RAW 264.7 macrophages, with an IC50 value of 6.61 ± 0.54 μM.

    7. Anhydrides

      Nano CuO Catalyzed Cross Dehydrogenative Coupling (CDC) of Aldehydes to Anhydrides

      Nilufa Khatun, Sourav Kumar Santra, Arghya Banerjee and Bhisma K. Patel

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejoc.201403508

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      An elegant synthesis of carboxylic acid anhydrides has been developed directly from arylaldehydes using CuO nanoparticles as the catalyst and tert-butyl hydroperoxide (TBHP) as the oxidant. During anhydride formation the reaction proceeds through a double sp2 C–H functionalization of aldehydes to generate two consecutive C–O bonds.

  26. Short Communications

    1. Dihaloalkenylsilanes

      Regio- and Stereoselective Synthesis of Vicinal (Z)-Dihaloalkenylsilanes from Silyl Ethynylarenes

      Yuta Yauchi, Masataka Ide, Ryo Shiogai, Takuya Chikugo and Tetsuo Iwasawa

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejoc.201403450

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      The highly regio- and stereoselective synthesis of vicinal (Z)-dihaloalkenylsilanes is successfully achieved by utilizing in situ prepared BrCl. BrCl is generated from readily available TMSCl and N-bromosuccinimide (NBS) and perfectly adds to silyl ethynylarenes in a syn mode. The resultant single isomer has significance in potential application as a multitunable synthetic scaffold.

  27. Full Papers

    1. Annulation

      N-Heterocyclic Carbene Catalyzed Generation and [4+2] Annulation of Unsubstituted Dienolate – Enantioselective Synthesis of Spirocyclic Oxindolodihydropyranones

      Jin-Tang Cheng, Xiang-Yu Chen, Zhong-Hua Gao and Song Ye

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejoc.201403395

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      The N-heterocyclic carbene catalyzed (NHC-catalyzed) generation of unsubstituted dienolate (butadienolate) and subsequent [4+2] annulation reactions with isatins afford chiral spirocyclic oxindolodihydropyranones in moderate yields with moderate to good enantioselectivities.

    2. Urea–Heterocycle Coupling

      Efficient and Selective Palladium-Catalysed C-3 Urea Couplings to 3,5-Dichloro-2(1H)-pyrazinones

      Anna Karin Belfrage, Johan Gising, Fredrik Svensson, Eva Åkerblom, Christian Sköld and Anja Sandström

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejoc.201403405

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      An efficient palladium-catalysed urea N-arylation protocol to install various functionalized ureas at the 3-position of the 2(1H)-pyrazinone is described. The procedure was used in the synthesis of a new inhibitor targeting the hepatitis C virus NS3 protease.

    3. Click Chemistry

      Synthesis of [(1,2,3-Triazol-1-yl)methyl]boronic Acids Through Click Chemistry: Easy Access to a Potential Scaffold for Protease Inhibitors

      Chiara Romagnoli, Emilia Caselli and Fabio Prati

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejoc.201403408

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      [(1,2,3-Triazol-1-yl)methyl]boronic acids, a new potential scaffold for protease inhibitors, have been synthesized by copper-catalyzed azide–alkyne cycloaddition reaction by starting from suitable azidomethylboronates.

    4. Reformatsky Chemistry

      Metal-Mediated Reformatsky Reaction of Bromodifluoromethyl Ketone and Imine

      Chun-Ru Cao, Min Jiang and Jin-Tao Liu

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejoc.201403424

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      An efficient method for the synthesis of β-amino α,α-difluoro ketones using the Reformatsky reaction of bromodifluoromethyl ketones with imines under mild conditions was developed. Using (S)-tert-butanesulfinyl as a chiral auxiliary, excellent diastereoselectivities were achieved in the asymmetric Reformatsky reactions.

    5. Friedel–Crafts Arylation

      Friedel–Crafts Arylation of α-Hydroxy Ketones: Synthesis of 1,2,2,2-Tetraarylethanones

      Anil Kumar, Tej V. Singh, Sajesh P. Thomas and Paloth Venugopalan

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejoc.201403438

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      An efficient Friedel–Crafts arylation of α-hydroxy ketones has been developed that allows access to a broader class of α-triaryl-substituted ketones. 2-Hydroxy-1,2,2-triarylethanones have been converted into 1,2,2,2-tetraarylethanones by using trifluoromethanesulfonic acid as Brønsted acid and arenes/heteroarenes as nucleophiles.

    6. Fluorinated Compounds

      Synthesis of 3-Fluoro-2-hetarylindoles and 3,3-Difluoro-2-hetarylindolines through Lewis Acid-Catalyzed Formation of 3,3-Difluoroindolium Ions

      Jacqueline Zi Mei Fong, Simon Sze Shiong Choo, Jean-Alexandre Richard, Marc V. Garland, Liangfeng Guo, Charles W. Johannes and Tuan Minh Nguyen

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejoc.201403443

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      A zinc triflate catalyzed three-step iminium sequence with in situ generation of indolium ions followed by addition of nucleophiles and dehydrofluorination has been developed. Arrays of 3-fluoro-2-hetarylindoles and 3,3-difluorohetarylindolines with different functional groups were subsequently synthesized in good yields. 3,3-Difluorohetarylindolines show interesting acidochromic properties.

    7. Carbolinephosphonates

      First Practical and Efficient Synthesis of 3-Phosphorylated β-Carboline Derivatives Using the Pictet–Spengler Reaction

      José Luis Viveros-Ceballos, Francisco J. Sayago, Carlos Cativiela and Mario Ordóñez

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejoc.201403418

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      We report the first practical and efficient synthesis of diethyl 1,2,3,4-tetrahydro-β-carboline-3-phosphonates and diethyl 9H-β-carboline-3-phosphonate derivatives. The target compounds were prepared in good yields using Pictet–Spengler reactions of phosphotryptophan diethyl ester with several aldehydes followed by oxidation chemistry.

    8. Amides

      2-Furanylboronic Acid as an Effective Catalyst for the Direct Amidation of Carboxylic Acids at Room Temperature

      Eric Kwok Wai Tam, Rita, Lionel Yiqian Liu and Anqi Chen

      Article first published online: 8 JAN 2015 | DOI: 10.1002/ejoc.201403468

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      Commercially available, inexpensive 2-furanylboronic acid has been identified as an effective catalyst for the direct dehydrative amide formation of carboxylic acids and amines. This transformation can be efficiently carried out at room temperature and is applicable to a wide range of carboxylic acids with primary and secondary amines to afford amides in good to excellent yields.

  28. Short Communications

    1. Energy Storage

      Naphthyridine Derivatives as a Model System for Potential Lithium–Sulfur Energy-Storage Applications

      Sebastian Resch, Anna-Rebekka Schneider, Ronja Beichler, Marcelle B. M. Spera, Jean Fanous, Dieter Schollmeyer and Siegfried R. Waldvogel

      Article first published online: 5 JAN 2015 | DOI: 10.1002/ejoc.201403542

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      The structure of a polyacrylonitrile-derived sulfur composite is elucidated by a bottom-up approach. New naphthyridine derivatives are synthesized as model systems for analytical comparison. The IR, NMR, and UV/Vis spectroscopy data indicate a strong correlation between this simple model compound and sulfurized polyacrylonitrile polymer.

    2. Dehydrogenative Heck Reaction

      Ligand-Promoted Reactivity of Alkenes in Dehydrogenative Heck Reactions of Furans and Thiophenes

      Alexandre Vasseur, Caroline Laugel, Dominique Harakat, Jacques Muzart and Jean Le Bras

      Article first published online: 5 JAN 2015 | DOI: 10.1002/ejoc.201403475

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      The all around influence of 4,5-diazafluorenone as a ligand enables the dehydrogenative Heck reaction of furans and thiophenes with hindered alkenes. Very high stereoselectivity can be achieved. The ligand has an influence on C–H bond activation, insertion of the alkene, the stereodetermining step, and the aerobic regeneration of the catalyst.

  29. Microreviews

    1. Guanidine Derivatives

      Synthetic Strategies for Preparing Bicyclic Guanidines

      Barbora Lemrová and Miroslav Soural

      Article first published online: 5 JAN 2015 | DOI: 10.1002/ejoc.201403185

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      Guanidine-based derivatives I with all three nitrogen atoms contained in two neighbouring cycles represent an interesting group of compounds with some unique properties. We describe the most important synthetic methods to prepare various target derivatives from different starting materials.

    2. Bicyclic Amino Acids

      Synthesis of [c]-Fused Bicyclic Proline Analogues

      M. Isabel Calaza, Francisco J. Sayago, Pedro Laborda and Carlos Cativiela

      Article first published online: 5 JAN 2015 | DOI: 10.1002/ejoc.201403121

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      This review describes synthetic methods devised to build [c]-fused bicyclic proline analogues. The focus is on the preparation of azabicycles containing a carbocyclic ring fused to the [c] face of the pyrrolidine unit. Attention is given both to procedures that afford the desired compounds in racemic form and to asymmetric strategies.

  30. Full Papers

    1. Peptide Conjugates

      Solid-Phase Synthesis of Peptide Conjugates Derived from the Antimicrobial Cyclic Decapeptide BPC194

      Sílvia Vilà, Esther Badosa, Emilio Montesinos, Lidia Feliu and Marta Planas

      Article first published online: 5 JAN 2015 | DOI: 10.1002/ejoc.201403344

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      An efficient methodology for the solid-phase synthesis of peptide conjugates by the linkage of BPC194 to a linear or cyclic sequence through a triazole ring is described.

    2. Enzyme Dual Activity

      Substrate Evaluation of Rhodococcus erythropolis SET1, a Nitrile Hydrolysing Bacterium, Demonstrating Dual Activity Strongly Dependent on Nitrile Sub-Structure

      Tracey M. Coady, Lee V. Coffey, Catherine O'Reilly and Claire M. Lennon

      Article first published online: 5 JAN 2015 | DOI: 10.1002/ejoc.201403201

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      The nitrile hydrolysing bacterial isolate Rhodococcus erythropolis SET1 has demonstrated dual nitrilase/NHase activity depending on the nitrile structure. β-Hydroxy nitriles unsubstituted α to the nitrile group gave acids along with recovered nitrile as a result of nitrilase activity of the isolate, whereas amides were the major product from α-vinyl β-hydroxy nitriles due to NHase activity.

    3. Acidity and Conformation

      Dependence of Stereoelectronic and Charge Effects on pKa Values of 1,3-Dithiane-Derived Sulfides, Sulfoxides, and Sulfones: An Experimental and Computational Investigation

      Bastian D. Süveges and Joachim Podlech

      Article first published online: 23 DEC 2014 | DOI: 10.1002/ejoc.201403409

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      Whereas the α-acidity of sulfoxides depends on the relative orientation of the acidic C–H and S=O bonds, this effect is significantly less pronounced in sulfones.

    4. Yne–Carbamate Cyclisation

      Efficient Synthesis of 5-Chalcogenyl-1,3-oxazin-2-ones by Chalcogen-Mediated Yne–Carbamate Cyclisation: An Experimental and Theoretical Study

      Alicia Monleón, Gonzalo Blay, Luis R. Domingo, M. Carmen Muñoz and José R. Pedro

      Article first published online: 23 DEC 2014 | DOI: 10.1002/ejoc.201403169

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      5-Chalcogenyl-1,3-oxazin-2-ones (chalcogenyl = SePh, SPh, TePh) have been synthesised in good yields and with total regioselectivity from chiral, non-racemic N-Cbz-protected propargylic amines through a 6-endo-dig cyclisation process. The experimental results have been rationalised by computational studies at the B3LYP/6-311G* level of theory.

    5. Arylation Reactions

      Lithium Choreography Determines Contrasting Stereochemical Outcomes of Aryl Migrations in Benzylic Carbamates, Ureas and Thiocarbamates

      Mark A. Vincent, Julien Maury, Ian H. Hillier and Jonathan Clayden

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejoc.201403572

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      The intramolecular arylation of lithiated derivatives of thiocarbamates proceeds with stereochemical retention because the sulfur–carbon interaction in the lithiated thiocarbamate enhances the stabilisation of the anion and its proximity to the migrating ring. The solvated lithium cation allows the carbanion to react with retention, whereas inversion is observed in the related carbamates.

    6. Spiro Compounds

      AlCl3-Catalyzed [3+2] Annulations of cis-2,3-Disubstituted Cyclopropane 1,1-Diesters with Cyclic Ketones: Diastereoselective Construction of Spirotetrahydrofurans

      Gaosheng Yang, Tingting Wang, Jun Chai and Zhuo Chai

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejoc.201403325

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      A series of highly functionalized spirotetrahydrofurans were easily accessed in stereomerically pure form by AlCl3-catalyzed [3+2] annulations of cis-2,3-disubstituted cyclopropane 1,1-diesters with cyclic ketones.

    7. Polycycles

      Complementary Synthetic Approaches to Elongated Polycyclic Arenes with Regioisomeric Carboxylic Substitution Patterns

      Harald Bock, Pauline Carré, Elizabeth A. Hillard and Fabien Durola

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejoc.201403339

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      Polycyclic arene-tetracarboxdiimides with a central anthracene moiety are accessible through Perkin condensations either from an anthrylene-diglyoxylic acid, a bromoaryl-acetic acid, or from a dibromophenylene-diacetic acid and an aryl-glyoxylic acid. The products of the latter path distinguish themselves by a particularly small optical band gap and long wavelength absorption.

    8. Helical Structures

      From Chrysene to Double [5]Helicenes

      Harald Bock, Stephanie Huet, Pierre Dechambenoit, Elizabeth A. Hillard and Fabien Durola

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejoc.201403341

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      Tetracarboxy-substituted double [5]helicenes are obtained from chrysene in four to six steps through Pd-catalyzed cyclizations. Their nonplanarity is manifest in the NMR spectra and leads to crystal packing with π-contacts in two dimensions. During the double cyclization of a disubstituted chrysene, Pd-catalyzed substituent migration is observed as side reaction.

    9. Synthetic Methodology

      A Route for the Total Synthesis of Enantiomerically Enriched Jasmonates 12-COOH-JA and 12-COOH-JA-Ile

      Clément F. Heinrich, Emilie Widemann, Jérémie Sanz, Raphaël Lugan, Thierry Heitz, Franck Pinot, Michel Miesch and Laurence Miesch

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejoc.201403347

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      A new synthetic route for enantiomerically enriched 12-COOH-JA and 12-COOH-JA-Ile from (+)-jasmonic acid is described. Ozonolysis afforded corresponding aldehydes that could be converted into 3-alkynoates. Z-Stereoselective reduction of the triple bond gave the desired compounds. N-tert-Butoxycarboxamide derivatives led to non-conjugated 12-COOH-JA, whereas free amides provided 12-COOH-JA-Ile.

    10. Asymmetric Reaction

      Chemo- and Stereoselective Reduction of β-Keto-α-oximino Nitriles by Using Baker's Yeast

      Kilwoong Mo, Soon Bang Kang, Youseung Kim, Yong Sup Lee, Jae Wook Lee and Gyochang Keum

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejoc.201403393

      Thumbnail image of graphical abstract

      The baker's yeast mediated reduction of β-keto-α-oximino nitriles at 20 °C afforded the corresponding β-hydroxy-α-oximino nitriles in high yields with high enantiomeric purity (enantiomeric excess value >99 %). The β-hydroxy-α-oximino nitriles were converted into α-hydroxy acid derivatives, and the oxime and nitrile groups were chemoselectively converted into other functionalities in high yields.

    11. Macrocycles

      The Reversible Nicholas Reaction in the Synthesis of Highly Symmetric Natural-Product-Based Macrocycles

      María C. de la Torre, María Asenjo, Pedro Ramírez-López and Miguel A. Sierra

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejoc.201403541

      Thumbnail image of graphical abstract

      Two complementary and efficient approaches to sophisticated natural-product-containing macrocycles by reversible Nicholas reactions are presented. Sophisticated (1:1) or (2:2) adducts are available either by keeping the acceptor–donor positions in the natural product moiety (DA–DA approach) or by putting the acceptor in the natural product moiety and the donor in the external reagent (DD–AD).

    12. Hydrogen Transfer

      A Metal-Catalyzed Tandem 1,4-Benzodiazepine Synthesis Based on Two Hydrogen-Transfer Reactions

      Varsha R. Jumde, Elena Cini, Andrea Porcheddu and Maurizio Taddei

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejoc.201403261

      Thumbnail image of graphical abstract

      Two consecutive Ru-catalyzed borrowing hydrogen processes offer an efficient method for benzodiazepine synthesis.

    13. Carbolines

      Synthesis and Properties of 5,7-Dihydropyrido[3,2-b:5,6-b′]diindoles

      Tran Quang Hung, Ngo Ngoc Thang, Do Huy Hoang, Tuan Thanh Dang, Khurshid Ayub, Alexander Villinger, Stefan Lochbrunner, Gerd-Uwe Flechsig and Peter Langer

      Article first published online: 22 DEC 2014 | DOI: 10.1002/ejoc.201403035

      Thumbnail image of graphical abstract

      5,7-Dihydropyrido[3,2-b:5,6-b′]diindoles were prepared by a highly efficient two-step synthesis that involved a site-selective Suzuki coupling reaction of 2,3,5,6-tetrabromopyridine and a subsequent Pd-catalyzed cyclization that proceeded through a twofold C–N coupling reaction with aromatic and aliphatic amines. R = n-C3H7.

    14. Directed Metalation

      Directed Functionalization of Halophenyl-2-oxazolines with TMPMgCl·LiCl

      João H. C. Batista, Fernanda M. dos Santos, Leandro A. Bozzini, Ricardo Vessecchi, Alfredo R. M. Oliveira and Giuliano C. Clososki

      Article first published online: 15 DEC 2014 | DOI: 10.1002/ejoc.201403255

      Thumbnail image of graphical abstract

      An efficient protocol was developed for the regioselective synthesis of difunctionalized aryl-2-oxazolines by employing the base TMPMgCl·LiCl (TMP = 2,2,6,6-tetramethylpiperidyl) in a directed metalation that takes place at room temperature followed by the addition of various electrophiles. The method allows for the isolation of the desired products in good yields.

  31. Microreviews

    1. Artificial Oxygenases

      Artificial Flavin Systems for Chemoselective and Stereoselective Oxidations

      Radek Cibulka

      Article first published online: 11 DEC 2014 | DOI: 10.1002/ejoc.201403275

      Thumbnail image of graphical abstract

      This review covers the design and applications of artificial flavinium-based organocatalytic systems for chemoselective and stereoselective oxygenations with hydrogen peroxide and oxygen as stoichiometric oxidising agents.

    2. Frondosin Natural Products

      The Frondosins: An Unusual Synthetic and Stereochemical Journey

      Michael D. VanHeyst and Dennis L. Wright

      Article first published online: 28 NOV 2014 | DOI: 10.1002/ejoc.201403116

      Thumbnail image of graphical abstract

      The first two syntheses of (+)-frondosin B, by Danishefsky and by Trauner, gave conflicting assignments for the single stereocenter at C8. Ensuing syntheses of frondosins B and A resolved this conflict and established that (+)-frondosin B is the R enantiomer. Wright's group showed that a late-stage stereochemical inversion occurred in a common intermediate of both their and Trauner's syntheses.

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